Fluoropropenyl oxadiazoles and the use thereof as pest control agents

ABSTRACT

The present invention relates to novel fluoropropenyl heterocycles of the formula (I) found 
     
         CF.sub.2 ═CX--CH.sub.2 -Het                            (1), 
    
     in which 
     Het, X and R are each as defined in the description, to processes for their preparation and to their use for controlling animal pests.

This application is a 371 of PCT/EP96/04663 filed Oct. 24, 1996.

The present invention relates to novel fluoropropenyl heterocycles, toprocesses for their preparation and to their use for controlling animalpests, in particular insects, arachnids and nematodes, encountered inagriculture, in forests, in the protection of stored products and ofmaterials, and in the hygiene sector.

It is already known that certain fluorobutenyl compounds havenematicidal activity (cf. for example WO 88/00183). However, theefficacy and the activity spectrum of these compounds, in particular atlow application rates and concentrations, are not always entirelysatisfactory.

This invention, accordingly, provides novel compounds of the formula (I)

    CF.sub.2 ═CX--CH.sub.2 -Het                            (I),

in which

X represents hydrogen or halogen,

Het represents one of the radicals ##STR1## and R representsrespectively optionally substituted alkyl, aryl, aralkyl or hetaryl.

Furthermore, it has been found that the compounds of the formula (I) areobtained when

A) amidoximes of the formula (II) ##STR2## in which R is as definedabove

are reacted with acyl chlorides of the formula (III)

    CF.sub.2 ═CX--CH.sub.2 --COCl                          (III),

in which

X is as defined above,

if appropriate in the presence of a diluent and if appropriate in thepresence of a base, and the resulting intermediates of the formula (IV)##STR3## in which R and X are each as defined above

are, if appropriate, isolated and, if appropriate, cyclized in thepresence of a base,

or

B) carbohydrazides of the formula (V)

    R--CONH--NH.sub.2                                          (V),

in which

R is as defined above

are reacted with acyl chlorides of the formula (III)

    CF.sub.2 ═CX--CH.sub.2 --COCl                          (III),

in which

X represents hydrogen or halogen,

in the presence of a diluent and in the presence of a base to givecompounds of the formula (VI)

    R--CONH--NH--CO--CH.sub.2 --CX═CF.sub.2                (VI)

in which

R and X are each as defined above,

and these compounds are, if appropriate, isolated and, if appropriate,cyclized in the presence of a diluent and, if appropriate, in thepresence of a dehydrating agent.

Finally, it has been found that the novel compounds of the formula (I)have pronounced biological properties and are suitable especially forcontrolling animal pests, in particular insects, arachnids andnematodes, encountered in agriculture, in forests, in the protection ofstored products and of materials, and in the hygiene sector.

The formula (I) provides a general definition of the compounds accordingto the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned hereinabove and hereinbelow are illustrated below.

X preferably represents hydrogen, fluorine or chlorine.

Het preferably represents one of the radicals or ##STR4## R preferablyrepresents C₁ -C₈ -alkyl, C₁ -C₈ -halogenylalkyl, C₁ -C₈ -alkoxy-C₁-C8-alkyl, C₁ -C₈ -alkylthio-C₁ -C₈ -alkyl, phenoxy-C₁ -C₄ -alkyl whichis optionally halogen-, C₁ -C₆ -alkyl-, C₁ -C₆ -alkoxy-, C₁ -C₆-halogenoalkyl- or C₁ -C₆ -halogenoalkoxy-substituted in the phenylmoiety,

preferably represents optionally halogen-, C₁ -C₆ -alkyl-, C₁ -C₆-alkoxy-, C₁ -C₆ -alkylthio-, C₁ -C₆ -halogenoalkyl-, C_(1-C) ₈-alkoxycarbonyl-, aminocarbonyl-, C₁ -C₆ -alkylaminocarbonyl-, di-C₁ -C₆-alkylaminocarbonyl-, nitro-, cyano- or SCN-substituted phenyl,

preferably represents phenyl-C₁ -C₄ -alkyl which is optionally halogen-,C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl-, C₁ -C₄ -alkoxy- or C₁ -C₄-alkylthio-substituted in the phenyl moiety, or

preferably represents optionally benzo-fused and optionally halogen-, C₁-C₆ -alkyl-, C₁ -C₆ -halogenoalkyl- or phenyl- (which is optionallysubstituted by halogen, C₁ -C₆ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-halogenoalkyl or C₁ -C₄ -halogenoalkoxy) substituted 5- or 6-memberedheteraryl having one or two hetero atoms from the group consisting ofoxygen, sulphur and nitrogen.

X particularly preferably represents hydrogen or fluorine.

Het particularly preferably represents one of the radicals ##STR5## Rparticularly preferably represents C₁ -C₄ -alkyl, C₁ -C₃ -halogenoalkyl,C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl,phenoxy-C₁ -C₂ -alkyl which is optionally fluorine-, chlorine-, C₁ -C₄-alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₃ -halogenoalkyl- or C₁ -C₃-halogenoalkoxy-substituted in the phenyl moiety,

particularly preferably represents optionally fluorine-, chlorine-, C₁-C₄ -alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio-, nitro- orcyano-substituted phenyl,

particularly preferably represents phenyl-C₁ -C₂ -alkyl which isoptionally fluorine-, chlorine-, C₁ -C₄ -alkyl-, or C₁ -C₂-halogenoalkyl-substituted in the phenyl moiety, or

particularly preferably represents respectively optionally benzo-fusedand optionally fluorine-, chlorine-, C₁ -C₄ -alkyl-, C₁ -C₂-halogenoalkyl- or phenyl- (which is optionally substituted by halogen,C₁ -C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₂ -alkoxy or C₁ -C₂-halogenoalkoxy) substituted furanyl, thienyl or pyridyl.

X very particularly preferably represents fluorine.

Het very particularly preferably represents one of the radicals ##STR6##R very particularly preferably represents C₁ -C₃ -alkyl, chloromethyl,trifluoromethyl, C₁ -C₄ -alkoxymethyl, C₁ -C₄ -alkylthiomethyl,phenoxymethyl which is optionally fluorine-, chlorine-, C₁ -C₃ -alkyl-,C₁ -C₃ -alkoxy-, trifluoromethyl- or trifluoromethoxy-substituted in thephenyl moiety,

very particularly preferably represents optionally fluorine-, chlorine-,C₁ -C₃ -alkyl-, C₁ -C₃ -alkoxy- or C₁ -C₃ -alkylthio-substituted phenyl,

very particularly preferably represents benzyl which is optionallyfluorine-, chlorine-, C₁ -C₃ -alkyl- or trifluoromethyl-substituted inthe phenyl moiety, or

very particularly preferably represents respectively optionallyfluorine-, chlorine-, C₁ -C₃ -alkyl- or trifluoromethyl- or phenyl-(which is optionally substituted by fluorine, chlorine, C₁ -C₃ -alkyl,trifluoromethyl or trifluoromethoxy) substituted furanyl, thienyl orpyridyl.

X most preferably represents fluorine.

Het most preferably represents one of the radicals ##STR7## R mostpreferably represents optionally fluorine-, chlorine-, methyl-, ethyl-,methoxy- or ethoxy-substituted phenyl or most preferably representsoptionally fluorine-, chlorine-, methyl- or ethyl-sustituted furanyl,thienyl or pyridyl.

The abovementioned general or preferred radical definitions orillustrations apply to the end products and, correspondingly, to thestarting materials and intermediates. These radical definitions can becombined with one another as desired, that is to say combinationsbetween the respective preferred ranges are also possible.

Preference according to the invention is given to those compounds of theformula (I) which contain a combination of the definitions listed aboveas being preferred (preferable).

Particular preference according to the invention is given to thosecompounds of the formula (I) which contain a combination of definitionslisted above as being particularly preferred.

Very particular preference according to the invention is given to thosecompounds of the formula (I) which contain a combination of thedefinitions listed above as being very particularly preferred.

Most particular preference according to the invention is given to thosecompounds of the formula (I) which contain a combination of thedefinitions listed above as being most particularly preferred.

In the radical definitions mentioned hereinabove and hereinbelow,hydrocarbon radicals such as alkyl or alkenyl are--including incombination with hetero atoms such as alkoxy oralkylthio--straight-chain or branched as far as this is possible.

Using 4-methylbenzamide oxime and 3,4,4-trifluorobut-3-enoyl chloride asstarting materials in the preparation of compounds of formula (I)according to process A), the course of the reaction can be representedby the following equation: ##STR8##

Using 4-chlorobenzhydrazide and 3,4,4-trifluorobut-3-enoyl chloride asstarting materials in the preparation of compounds of the formula (I)according to process B), the course of the reaction can be representedby the following equation: ##STR9##

The process A) according to the invention for preparing compounds of theformula (I) is characterized in that initially amidoximes of the formula(II) are reacted with acyl chlorides of the formula (III), ifappropriate in the presence of a base.

Diluents which are suitable for this purpose are organic solvents.Examples include hydrocarbons such as cyclohexane, toluene or benzene,halogenated, in particular chlorinated, hydrocarbons such as methylenechloride, chloroform, dichloroethane or chlorobenzene and furthermorenitriles such as acetonitrile.

The reaction of the amidoximes of the formula (II) with the acylchlorides of the formula (III) is preferably carried out in the presenceof a base. Suitable bases are organic bases, in particular tertiaryamines such as diazabicycloundecane (DBU), diazabicyclononene (DBN),diazabicyclooctane (DABCO), pyridine or triethyleneamine, and alsoinorganic bases, in particular alkali metal or alkaline earth metalcarbonates, bicarbonates, hydroxides or oxides such as potassiumcarbonate, sodium bicarbonate, sodium hydroxide or calcium oxide, Ingeneral, it is not necessary to isolate the intermediates of the formula(IV). They can be converted into the desired 1,2,4-oxadiazoles forexample by prolonged heating and/or in the presence of theabovementioned bases.

The reaction temperature in the process A) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between -10° C. and 180° C., preferablybetween 0° C. and 140° C.

In general, the starting materials of the formulae (II) and (III) areemployed in approximately equimolar amounts, however, it is alsopossible to use one component or the other in a relatively large excess(up to about 2:1).

In general, at least an equimolar amount of the base is also added.

The process A) according to the invention is generally carried out underatmospheric pressure (cf. Houben-Weyl, Methoden der organischen Chemie,Vol. E 8c, part 3, p. 409 ff).

The process B) according to the invention for preparing compounds of theformula (I) is characterized in that carbohydrazides of the formula (II)are initially reacted with acyl chlorides of the formula (III) in thepresence of a diluent and in the presence of a base to give thediacylhydrazines of the formula (VI) (step 1), which are, ifappropriate, isolated and, if appropriate, cyclized in the presence of adiluent and, if appropriate, in the presence of a dehydrating agent(step 2).

Diluents which are suitable for step 1 of the process B) according tothe invention are organic solvents. Examples include aliphatic oraromatic, optionally halogenated (in particular chlorinated)hydrocarbons such as cyclohexane, toluene, xylene, dichloromethane,trichloromethane, dichloroethane or chlorobenzene, ethers such astetrahydrofuran or dioxane, nitriles such as acetonitrile, amides suchas dimethylformamide or sulphoxides such as dimethyl sulphoxide.

The reaction can also be carried out in a two-phase system consisting ofwater and an organic solvent such as water/dichloromethane orwater/toluene.

Suitable bases for step 1 of the process B) according to the inventionare both organic bases, in particular tertiary amines such as DBU, DBN,DABCO, pyridine or triethylamine, and inorganic bases, in particularalkali metal carbonates, bicarbonates or hydroxides such as sodiumcarbonate, potassium carbonate, sodium bicarbonate or sodium hydroxide.

The intermediates of the formula (VI) can be isolated prior to step 2(cyclization) of the process B) according to the invention. However, itis also possible to carry out these steps directly after step 1, i.e.without isolation of the intermediates of the formula (VI).

Step 2 of the process B) according to the invention (cf. Houben-Weyl,Methoden der org. Chemie, Vol. E 8c, part 3, p. 563 ff) is preferablycarried out in the presence of a diluent. Suitable diluents are inertorganic solvents, for example optionally halogenated (chlorinated)hydrocarbons such as toluene, xylene or dichlorobenzene or amides suchas dimethylacetamide.

Step 2 of the process B) according to the invention is carried out inthe presence of a dehydrating agent. Suitable dehydrating agents are thecustomary dehydrating agents. Examples include phosphorus oxychloride,polyphosphoric acid, p-toluenesulphonic acid and phosphorus pentoxide.

It may be advantageous to carry out the reaction in an apparatuscomprising a water separator.

The reaction temperature in the process B) according to the inventioncan be varied within a relatively wide range. In general, the reactionis carried out at temperatures between 0° C. and 200° C., preferablybetween 20° C. and 150° C.

The temperature at which step 1 is carried out may differ from thetemperature at which step 2 is carried out (cf. Preparation Examples).

In general, the starting materials of the formula (III) and (V) areemployed in approximately equimolar amounts, however, it is alsopossible to employ one component or the other in a relatively largeexcess (up to 3:1, preferably up to 1.5:1).

In general, at least an equimolar amount of base is also added.

The process B) according to the invention is generally carried out underatmospheric pressure.

The intermediates of the formula (VI) can also be prepared by reactingcarbohydrazides of the formula (VII)

    CF.sub.2 ═CX--CH.sub.2 --CO--NH--NH.sub.2              (VII)

in which

X is as defined above

with acyl chlorides of the formula (VIII)

    R--COCl                                                    (VIII)

in which

R is as defined above.

This reaction can be carried out under the reaction conditions describedabove under step 1 of the process B) according to the invention.

The amidoximes of the formula (II) required as starting materials andthe carbohydrazides of the formula (V) are known and/or can be preparedby generally known methods (see for example Houben-Weyl, Methoden derorganischen Chemie. Vol. (VIII), p. 676; F. Eloy, R. Lenaers, Chem. Rev.62, 155 (1962)).

The acyl chlorides of the formula (III) furthermore required as startingmaterials are known (see for example U.S. Pat. No. 5,389,680 and EP 0432 861).

The active compounds are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, encountered in agriculture,in forests, in the protection of stored products and of materials, andin the hygiene sector. They can preferably be employed as cropprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Spodoptera litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella. Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp. and Trichodorus spp.

The compounds of the formula (I) according to the invention inparticular have outstanding nematicidal activity, for example againstMeloidogyne incognita. They have good folar insecticidal action.

The active compounds according to the invention act systemically.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspo-emulsionconcentrates, natural and synthetic materials impregnated with activecompound and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, if appropriate with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. Essentially, thefollowing are suitable liquid solvents: aromatics, such as xylene,toluene or alkylnaphthalenes, chlorinated aromatics and chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetableoils, alcohols, such as butanol or glycol and their ethers and esters,ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, and water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,as well as synthetic granules of inorganic and organic meals, andgranules of organic material such as sawdust, coconut shells, maize cobsand tobacco stalks; suitable emulsifiers and/or foam-formers are: forexample nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand protein hydrolysates; suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Possible furtheradditives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations. as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fungicides, growth-regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas and substances produced bymicroorganisms, inter alia.

Examples of particularly advantageous mixing components are thefollowing:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl }-3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate; 2-phenylphenol (OPP), aldimorph,ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl,binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole,bupirimate, buthiobate, calcium polysulphide, captafol, captan,carbendazim, carboxin, quinomethionate, chloroneb, chloropicrin,chlorothalonil, chlozolinate, cufraneb, cymoxanil, cypro-conazole,cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos,dithianon, dodine, drazoxolon, edifenphos, epoxyconazole, ethirimol,etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide,fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol,folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl,furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazol,imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane, kasugamycin, copper preparations such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb,maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene(PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam,tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl,thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaiicides/Nematicides

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichiofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonofos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH,heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,lambda-cyhalothrin, lufenuron, malathion, mecarbam, mervinphos,mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemeton M,oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozine, pyrachlofos, pyradaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, RH 5992,salithion, sebufos, silafluofen, sulfotep, suiprofos, tebufenozide,tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temephos,terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,thiomethon, thionazin, thuringiensin, tralomethrin, triarathene,triazophos, triazuron, trichiorfon, triflumuron, trimethacarb,vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth-regulators is also possible.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergists.Synergists are compounds which increase the action of the activecompounds, without it being necessary for the synergist added to beactive itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene and stored-product pests, the active compoundhas excellent residual action on wood and clay and good stability toalkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as ixodid ticks, argasid ticks, scab mites, trombiculid mites,flies (stinging and sucking), parasitic fly larvae, lice, hair lice,bird lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andlschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the sub-orders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which attack agriculturallivestock, such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese,honey bees, other domestic animals, such as, for example, dogs, cats,caged birds, aquarium fish, and so-called experimental animals, such as,for example. hamsters, guinea-pigs, rats and mice. By controlling thesearthropods, it is intended to reduce mortality and decreasedperformances (in meat, milk, wool, hides, eggs, honey and the like), sothat more economical and simpler animal keeping is possible by using theactive compounds according to the invention.

In the veterinary sector, the active compounds according to theinvention are used in a known manner by enteral administration, forexample in the form of tablets, capsules, drinks, drenches, granules,pastes, boluses, the feed-through method, suppositories, by parenteraladministration, such as, for example, by means of injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal administration, forexample in the form of dipping or bathing, spraying, pouring-on andspotting-on, washing, dusting, and with the aid of shaped articles whichcomprise active compound, such as collars, ear tags, tail marks, limbbands, halters, marking devices and the like.

When administered to livestock, poultry, domestic animals and the like,the active compounds of the formula (I) can be used as formulations (forexample powders, emulsions, flowables) which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after dilutionby a factor of 100 to 10 000, or they may be used in the form of achemical bath.

The preparation and the use of the active compounds according to theinvention are illustrated by the examples below.

PREPARATION EXAMPLES Example 1 ##STR10##

At 20° C., 6.0 g (38 mmol) of 3,4,4-trifluorobutenoyl chloride are addeddropwise to a solution of 6.0 g (40 mmol) of 4-methylbenzamide oxime in60 ml of dioxane and 4.9 g (62 mmol) of pyridine, and the mixture issubsequently stirred at 90° C. for 12 h. The mixture is then poured intowater, the product is extracted with methylene chloride and the organicphase is concentrated under reduced pressure.

The crude product thus obtained is chromatographed over silica gel usingthe system chloroform/ethyl acetate =4:1. 5.5 g (57% yield of theory) ofcrystalline3-(4-methylphenyl)-5-(2,3,3-trifluoroprop-2-enyl)-1,2,4-oxadiazole ofmp. 46-50° C. are obtained.

Example 2 ##STR11##

4.0 g (13.7 mmol) of1-(4-chlorobenzoyl)-2-(3,3,4-trifluoro-but-3-enoyl)-hydrazine in 50 mlof toluene are heated under reflux with 4.2 g (27.4 mmol) of phosphorusoxychloride for 1 h. The toluene is subsequently removed under reducedpressure and the residue is taken up in methylene chloride/ice-water.The organic phase is concentrated under reduced pressure and purified bysilica gel column chromatography using the system chloroform/ethylacetate (9:1). 2.3 g (64.5% yield of theory) of2-(4-chlorophenyl)-5-(2,3,3-trifluoroprop-2-enyl)-1,3-4-oxadiazole ofmp. 72° C. are obtained.

Prepartion of the Starting Materials ##STR12##

5.2 g (30.3 mmol) of 4-chlorobenzhydrazide in 50 ml of dichloromethaneare admixed with a solution of 2.8 g (33 mmol) of sodium bicarbonate in25 ml of water, and 4.8 g (30.3 mmol) of 3,4,4-trifluorobut-3-enoylchloride are subsequently added with stirring at 0° C. After stirringovernight, the precipitated1-(4-chlorobenzoyl)-2-(3,4,4-trifluorobut-3-enoyl)-hydrazine is filteredoff with suction.

Yield: 8.0 g (90.4% of theory) of mp. 198° C.

Similar to Examples 1 and 2 and/or according to the general preparationprocedures, the compounds of the formula (I) listed in the table belowwere obtained.

    __________________________________________________________________________    Ex. No.                                                                           Formula                   Physic. Data                                    __________________________________________________________________________      3                                                                                                           log p* #                                                                    = 3.44 (pH 2)                                      - 4                                                                                                        log p = 2.08                                     - 5                                                                                                        log p = 3.30 (pH 2)                              - 6                                                                                                        log p = 4.72 (pH 2)                              - 7                                                                                                        log p = 3.20 (pH 2)                              - 8                                                                                                        log p = 2.46 (pH 7.5)                            - 9                                                                                                        log. p = 1.89 (pH 7.5) n.sub.D.sup.20 =                                     1.4980                                             - 10                                                                                                       log p = 2.19 (pH 7.5) n.sub.D.sup.20 =                                      1.5304                                          __________________________________________________________________________     *log p: logarithm to base ten of the noctanol/water partition coefficient     determined by reverse phase HPLC analysis using H.sub.2 O/CH.sub.3 CN.   

Use Example Example A

Critical Concentration Test/Nematodes

    ______________________________________                                        Test nematode:                                                                            Meloidogyne incognita                                               Solvent: 4 parts by weight of acetone                                         Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The active compound preparation is intimately mixed with soil which isheavily infested with the test nematodes. The active compoundconcentration in the preparation is immaterial, only the amount ofactive compound per unit volume of soil, which is given in ppm (=mg/l),matters. The treated soil is transferred into pots, lettuce seeds aresown, and the pots are kept at a greenhouse temperature of 25° C.

After four weeks, the lettuce roots are checked for infestation withnematodes (root galls) and the efficacy of the active compound in % isdetermined. The efficacy is 100% when infestation is avoided completelyand 0% when the infestation level is just as high as in the controlplants in untreated, but equally infested, soil.

In this test, an efficacy of 100% was shown, for example, by thecompound of Preparation Example 10, at an exemplary active compoundconcentration of 20 ppm.

Example B

Phaedon Larvae Test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                              Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into theactive compound preparation of the desired concentration and arepopulated with mustard beetle larvae (Phaedon cochleariae) while theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all the beetle larvae have been killed, 0% means that none ofthe beetle larvae have been killed.

In this test, a kill of 100% is shown, after 7 days, for example, by thecompounds of Preparation Examples 1, 2 and 7, at an exemplary activecompound concentration of 0.1%.

Example C

Plutella Test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                              Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into theactive compound preparation of the desired concentration and arepopulated with caterpillars of the diamond back moth (Plutellaxylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all the caterpillars have been killed, 0% means that none ofthe caterpillars have been killed.

In this test, a kill of at least 90% was shown, after 7 days, forexample, by the compounds of Preparation Examples 1, 2, 3, 5, 7 and 8,at an exemplary active compound concentration of 0.1%.

Example D

Spodoptera Test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                              Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into theactive compound preparation of the desired concentration and arepopulated with caterpillars of the owlet moth Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all the caterpillars have been killed, 0% means that none ofthe caterpillars have been killed.

In this test, a kill of at least 85% was shown, after 7 days, forexample, by the compounds of Preparation Examples 1, 3 and 7, at anexemplary active compound concentration of 0.1%.

Example E

Nephotettix Test

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                              Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryzae sativa) are treated by being dipped into theactive compound preparation of the desired concentration and arepopulated with larvae of the green rice leaf hopper (Nephotettixcincticeps) while the seedlings are still moist.

After the desired period of time, the kill in % is determined. 100%means that all the leaf hoppers have been killed; 0% means that none ofthe leaf hoppers have been killed.

In this test, a kill of 100% was shown, after 6 days, for example, bythe compounds of Preparation Examples 1, 2 and 3, at an exemplary activecompound concentration of 0.1%.

Example F

Myzus Test (Duration of Activity after Spraying)

    ______________________________________                                        Solvent:    7 parts by weight of dimethylformamide                              Emulsifier: 1 part by weight of alkylaryl polyglycol ether                  ______________________________________                                    

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean shoots (Vicia faba) which are heavily infested by the black beanaphid (Aphis fabae) are treated by being dipped into the active compoundpreparation of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed, 0% means that none of the aphidshave been killed.

In this test, a kill of 90% and 80% was shown, for example, by thecompounds of Preparation Examples 1, and 2, respectively, at anexemplary active compound concentration of 0.1%.

Example G

Test with Fly Larvae/Development-Inhibitory Action

    ______________________________________                                        Test animals:                                                                          all larval stages of Lucilia cuprina (OP resistent)                     [pupae and adults (without contact with the active                            compound)]                                                                   Solvent: 35 parts by weight of ethylene glycol monomethyl ether                        35 parts by weight of nonylphenol polyglycol ether                 ______________________________________                                    

To produce a suitable preparation, 3 parts by weight of the activecompound are mixed with 7 parts by weight of the abovementionedsolvent-emulsifier mixture, and the resulting emulsion concentrate isdiluted with water to the concentration desired in each case.

For each concentration, 30 to 50 larvae are introduced into a test tubewhich contains horse meat (1 cm³). 500 μl of the dilution to be testedare pipetted onto this horse meat. The test tubes are placed in plasticbeakers whose bottom is covered with sea sand, and kept in anair-conditioned room (26° C.±1.5° C., 70%±10% relative humidity). Theactivity is examined (larvicidal action) after 24 hours and 48 hours.After emergence of the larvae (about 72 h), the test tubes are removedand perforated plastic lids are fitted onto the beakers. After 1.5 timesthe development time (hatching of control flies), the hatched flies andthe pupae/cocoons are counted.

The activity criterion is the incidence of death in the treated larvaeafter 48 h (larvicidal effect), or the inhibition of hatching of adultsfrom pupae or the inhibition of pupae formation. The criterion for thein vitro activity of a substance is the inhibition of the development ofthe fleas, or a development standstill before the adult stage. 100%larvicidal action means that all the larvae have been killed after 48hours. 100% development-inhibitory action means that no adult flies havehatched.

In this test, an activity of 100% was shown, for example, by thecompounds of Preparation Examples 3, 5 and 7, at an exemplary activecompound concentration of 1000 ppm.

Example H

Test with Boophilus Microplus Resistent/SP-Resistent Parkhurst Strain

    ______________________________________                                        Test animals:                                                                            Adult females which have sucked themselves full                      Solvent: Dimethyl sulphoxide                                                ______________________________________                                    

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,and lower concentrations are prepared by diluting in the same solvent.

The test is carried out in 5 replications. I μl of the solutions isinjected into the abdomen, and the animals are transferred into dishesand kept in an air-conditioned room. The activity is determined via theinhibition of oviposition. 100% means that no tick has deposited eggs.

In this test, an activity of 100% was shown, for example, by thecompound of Preparation Example 1, at an exemplary active compoundconcentration of 200 μg/animal.

We claim:
 1. A compound of the formula (I)

    CF.sub.2 ═CX--CH.sub.2 --Het                           (I),

in which X represents hydrogen or halogen, Het represents one of theradicals ##STR21## and R represents respectively optionally substitutedalkyl, aryl, aralkyl or heteroaryl.
 2. A process for preparing thecompound of the formula (I) according to claim 1, whereinA) amidoximesof the formula (II) ##STR22## in which R is as defined in claim 1 arereacted with acyl chlorides of the formula (III)

    CF.sub.2 ═CX--CH.sub.2 --COCl                          (III),

in whichX is as defined in claim 1, optionally in the presence of adiluent and optionally in the presence of a base, and the resultingintermediates of the formula (IV) ##STR23## in which R and X are each asdefined above are optionally isolated and cyclized in the presence of abase,or B) carbohydrazides of the formula (V)

    R--CONH--NH.sub.2                                          (V),

in whichR is as defined above are reacted with acyl chlorides of theformula (III)

    CF.sub.2 ═CX--CH.sub.2 --COCl                          (III),

in whichX represents hydrogen or halogen, in the presence of a diluentand in the presence of a base to give compounds of the formula (VI)

    R--CONH--NH--CO--CH.sub.2 --CX═CF.sub.2                (VI)

in whichR and X are each as defined above, and these compounds areoptionally isolated and cyclized in the presence of a diluent andoptionally in the presence of a dehydrating agent.
 3. A pesticidalcomposition comprising at least one compound of the formula (I)according to claim 1 and an extender.
 4. A method of combating unwantedpests which comprises administering to such pests or to a locus fromwhich it is desired to exclude such pests a pesticidally effectiveamount of a compound according to claim 1.